Thermal protective composition and method of protecting a substrate from hyperthermal conditions

ABSTRACT

A composite system capable of protecting a substrate from a jet fire including a lower layer of an active fire protective material and an upper layer of a fire protective material. The upper layer forms an open cell matrix when exposed to a jet fire to permit passage of gasses from the lower layer to ambient. The upper layer comprises a fill of refractory material and protects the system during initial exposure to a hyperthermal condition. The upper layer swells on exposure to hyperthermal conditions, but swells less than the lower layer.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of application Ser. No. 10/036,717,filed Dec. 21, 2001, now U.S. Pat. No. 6,855,401, which claims thebenefit of United States Provisional application 60/258,138 filed Dec.22, 2000, the disclosures of which are hereby incorporated by reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not applicable.

BACKGROUND OF THE INVENTION

This invention relates to thermal protective coatings. It isparticularly useful as applied to coatings which are applied tosubstrates to protect the substrate from extremely high intensity, highvelocity hyperthermal conditions.

Various compositions are known which provide protection against fire andother thermal extremes. Presently, such compositions generally include apolymeric binder and form a char when exposed to fire or hyperthermalconditions. The char-forming compositions may operate by variousmodalities. Several char-forming, fire-resistive coatings are describedin Deogon, U.S. Pat. No. 5,591,791. Briefly, such coatings includeablative coatings, which swell to less than twice their originalthickness when exposed to fire or other thermal extremes, intumescentcoatings such as those disclosed in Nielsen et al., U.S. Pat. No.2,680,077, Kaplan, U.S. Pat. No. 3,284,216, or Ward et al., U.S. Pat.No. 4,529,467, which swell to produce a char more than five times theoriginal thickness of the coating, and subliming char-forming coatingsof the type disclosed in Feldman, U.S. Pat. No. 3,849,178, which undergoan endothermic phase change and expand two to five times their originalthickness to form a continuous porosity matrix. The intumescent andsubliming coatings are denoted “active” thermal protective coatings. Thecoatings are also sometimes applied to an intermediate structure whichis then applied to the substrate as set out in Feldman, U.S. Pat. No.4,493,945.

The time required for a given temperature rise across a predeterminedthickness of the composition, under specified heat flux, environmental,and temperature conditions, is a measure of the composition'seffectiveness in providing thermal protection to an underlyingsubstrate.

Eventually, the char is consumed by physical erosion and by chemicalprocesses, such as oxidation by oxygen in the air and by free radicalsproduced by the coating or otherwise in a fire environment, andprotection is substantially reduced. Before the char is totallyconsumed, degradation of the char layer leaves it crumbled and withoutthe necessary strength to sustain itself, causing it to fail by beingblown off or simply falling off (spalling).

Various methods and structures have also been used or proposed forapplying these thermal protective coating materials. The most frequentapproach is to apply the materials directly to the substrate, withoutadditional structure. For many applications, however, a reinforcingmaterial, such as fiberglass fabric, graphite fabric, or a wire mesh,has been embedded in the coating material to strengthen the material andprevent it from cracking or falling off the substrate under conditionsof flame or thermal extreme. Examples of this approach are found inFeldman, U.S. Pat. No. 3,022,190, Billing et al, U.S. Pat. No.3,913,290, Kaplan, U.S. Pat. No. 3,915,777, and Billing et al, U.S. Pat.No. 4,069,075. Sometimes the materials are first applied to areinforcing structure such as a flexible tape or flexible wire mesh, andthe combined structure is applied to the substrate. Examples of thisapproach are found in Feldman, U.S. Pat. No. 3,022,190, Pedlow, U.S.Pat. No. 4,018,962, Peterson et al, U.S. Pat. No. 4,064,359, Castle,U.S. Pat. No. 4,276,332, and Fryer et al, U.S. Pat. No. 4,292,358. Inthese last-mentioned systems, the purpose of the reinforcing structuremay be both to strengthen the resulting composite and to permit itsapplication to a substrate without directly spraying, troweling orpainting the uncured coating materials onto the substrate. In any of theforegoing methods and structures, multiple layers are frequently appliedto the substrate to provide additional protection.

Presently known materials and methods, however, are not as efficient, interms of length of protection for a given weight of protective material,as desirable. Efficiency is particularly important because in manyapplications weight or volume is critically limited. Moreover, heavilyloading coating materials with fire retardants may seriously impairtheir physical characteristics and otherwise limit their suitability ascoatings, for example by limiting their film-forming characteristics ortheir water-resisting characteristics.

Under certain extreme fire conditions, all of these known coatingsystems have required excessive thickness and weight to provide adequateprotection. One of the environments in which such extreme fireconditions can occur is in the vicinity of a delivery pipe carryingflammable compressed gas or liquid, typically a hydrocarbon, from onelocation to another location. A rupture in the pipe or a failure of avalve or joint can result in a high-temperature, high heat flux,high-velocity flame, frequently termed a “jet fire.” If the differencein pressure across the rupture or opening is greater than abouttwo-to-one, a choked flow condition is produced at the aperture, and asupersonic flow of gas is produced downstream of the aperture. The heatflux of these high velocity gases is on the order of about 300 to 320kilowatts per square meter, and the temperature can typically be from1,000° C. to 1,500° C. There have been standards produced which define ajet fire and delineate test procedures for assessing the effectivenessof protective coating systems. An important standard is identified asOTI 95 634 “Jet Fire Resistance Test Of Passive Fire ProtectionMaterials” (Health and Safety Executive (UK), Offshore TechnologyReport, 1996). This document is incorporated herein by reference.

When exposed to the temperatures, heat fluxes, and aerodynamic shearforces of a jet fire, presently known coating systems erode and arequickly consumed or spall and fall off. Ablative coatings tend toproduce dense chars having good physical and chemical resistance, but instandard jet fire tests they have been found to allow an underlyingsubstrate to reach the critical temperature in a very short time. In thecase of active coatings which swell when exposed to thermal extremes,the degradations are usually in the form of fissures which are formed inthe char as a result of differential thermal stresses produced by thehigh thermal gradients and rapid erosion caused by shear forces.

To increase the strength of char layers during exposure to thermalextremes, and to limit spalling and fissures, fabrics have long beenincorporated in the coating materials. As set out in Feldman et al.,U.S. Pat. No. 5,622,774, fiberglass fabric provides an inexpensive, easyto install, reinforcement in many high temperature applications. Jetfires, however, raise the fabric to temperatures above the softeningpoint of the glass (around 870° C.), and the fiberglass fabric hasdisintegrated. Other fabrics have therefore been required. Graphitecloth, as taught in the foregoing Feldman et al., U.S. Pat. No.5,622,774, and in Castle et al., U.S. Pat. No. 5,580,648, Boyd et al.,U.S. Pat. No. 5,433,991, and Kobayashi et al., U.S. Pat. No. 5,401,793,is one choice. The graphite cloth may be either substantially purecarbon or a precursor material, as is well-known in the art. Refractorymaterials, such as quartz (Refrasil) fabric, are also used. Metal meshis inexpensive and widely used, but it is heavy and difficult toinstall. Even when reinforced with fabric or mesh, however, knownprotective systems are not very efficient in protecting against a jetfire and therefore require thick, heavy coatings to provide even limitedprotection.

The patents mentioned herein are all incorporated herein by reference.

BRIEF SUMMARY OF THE INVENTION

One of the objects of one embodiment of the present invention is toprovide a thermal protective system which is more efficient inprotecting against jet fires than presently known system.

Other objects will become apparent to those skilled in the art in lightof the following description.

In accordance with one aspect of the present invention, generallystated, a composite system capable of protecting a substrate from a jetfire is provided, the system comprising a lower layer of an active fireprotective material and an upper layer of an ablative fire protectivematerial, the ablative material forming an open cell matrix when exposedto a jet fire to permit passage of gasses from the lower layer toambient.

In accordance with another aspect of the present invention, generallystated, a composite system capable of protecting a substrate from a jetfire is provided comprising a lower layer of an active fire protectivematerial which swells when exposed to a fire or other hyperthermalcondition and an upper layer of an active fire protective material whichswells when exposed to a fire or other hyperthermal condition, the upperlayer swelling less than the lower layer, the upper layer comprising afill of refractory material comprising at least about seven percent ofthe upper layer by weight.

In accordance with another aspect of the invention, a method forprotecting a substrate from hyperthermal conditions is providedcomprising a first step of applying a layer of a first active thermalprotective composition to the substrate, and thereafter a second step ofapplying an upper layer of a second active thermal protectivecomposition to the first layer, the second composition comprising a fillof a refractory material comprising at least about seven percent of thesecond composition by weight. Preferably, both the first composition andthe second composition comprise a polymeric binder and a gas former, thesecond composition comprising less gas former by weight than the firstcomposition.

In some embodiments, a high-temperature mesh or fabric reinforcement isembedded in the composite system. The reinforcement may be of numerousmaterials. In one embodiment it is graphite. In another it is metal,such as galvanized steel. In others it is fiberglass of various types; ahigh temperature polymer such as polyimide, polybenzoimidazole, orpolyamide such as Kevlar; a ceramic such as silica or zirconia; or asilicone, or a combination of these materials. Other mesh or fabricreinforcements may also be used, and the reinforcement may befree-floating in the composite or pinned to the underlying substrate. Insome embodiments, the mesh or fabric is applied to the lower layereither before or after the lower layer has substantially cured. If thelower layer has substantially cured, an adhesive layer, preferably inthe form of a thin coat of the uncured upper layer, may be applied tothe lower layer, and the mesh or fabric is embedded in the adhesivelayer. In other embodiments, the mesh or fabric is embedded in the upperlayer. In other embodiments, the mesh or fabric is embedded in the lowerlayer. In other embodiments, particularly when a mesh is pinned to thesubstrate and the thickness of the system is low, the mesh may extendthrough into both layers of the system. In other embodiments, the amountand size of chopped fibers in the upper layer is chosen to substitutefor the mesh or fabric. In other embodiments, no mesh or fabricreinforcement is required because of the requirements of the system. Inother embodiments, the mesh or fabric is utilized to set the system offfrom the substrate as in Feldman, U.S. Pat. No. 4,493,945.

In the preferred embodiments of the composite system, the lower layer isapplied directly to the substrate and adheres to it. It will of coursebe understood that a primer is generally first applied to the substrateto aid in adherence, in accordance with generally accepted practice.

In the preferred embodiments, the lower layer is about 1-25 mm thick. Inone embodiment, the lower layer is less than 15 mm thick. In anotherembodiment, the lower layer is about 3 mm to about 10 mm thick.

The lower layer responds to hyperthermal conditions by expanding to atleast twice its original thickness. In some embodiments, the lower layerexpands about two to about five times its applied thickness. In otherembodiments, the lower layer expands from five to one hundred times itsoriginal thickness. The lower layer preferably includes about 30% toabout 65% polymeric resin and more than 30% blowing agent (gas former).Numerous useable formulations are known in the art, some examples beinggiven in the foregoing patents. Another is given in McGinniss et al.,U.S. Pat. No. 5,487,946. Others are commercially available, for exampleChartek 7 (Akzo Nobel/international Paint, Ltd.), Albi Clad 800 (AlbiManufacturing division of Stanchem, Inc.), or Thermo-Lag 3000,Thermo-Lag 2000, Thermo-Lag 440, Thermo-Lag 330, or Thermo-Lag 220(Nu-Chem, Inc.)

In the preferred embodiments, the upper layer is about 1-25 mm thick. Inone embodiment, the upper layer is less than 15 mm thick. In anotherembodiment, the upper layer is about 2 mm to about 6 mm thick. When meshor fabric reinforcement is used, it is preferred that the upper layer beat least about 2.5 mm thick.

The upper layer composition forms a part of the present invention bothin combination with the lower layer and per se. Thus, in accordance withanother aspect of the invention, a thermally protective composition isprovided having a polymeric binder, from 5% to 30% of a blowing agentwhich changes from solid to gas at a hyperthermal temperature to whichthe composition may be subjected, and at least 7% of a refractoryfiller.

The refractory filler preferably includes particles or fibers, or both.The fillers preferably comprise glass, graphite, or ceramic fibers andparticles (granules). The glass may be of various types. The ceramic mayinclude, for example, metal oxides such as silica, alumina, mullite,magnesium oxide, titanium dioxide, and zirconia; metal carbides such assilicon carbide, aluminum carbide, boron carbide, and zirconium carbide;metal nitrides such as silicon nitride, boron nitride, and aluminumnitride; metal silicates such as aluminum silicate, cordierite, zircon,and steatite; and metal borides such as silicon tetraboride, tungstenboride, and zirconium boride. The graphite may be in the form ofsubstantially pure carbon or may be a precursor material which convertsto substantially pure carbon under fire conditions. Any fibers should belimited in length to no more than about 7 mm for use in present-dayspray applicators, but longer fibers may be used when the upper layer isapplied by other methods such as troweling, brushing, rolling, ormolding. In one embodiment, the fillers comprise at least about 15% byweight of the composition. In another embodiment they comprise about 20%to 30%, by weight of the composition. In other embodiments they compriseat least 25% by weight of the composition. The inert fillers increasethe erosion resistance of the system and greatly increase itseffectiveness. The inert fillers are preferably chosen to reradiate heat(as by reflection) from a high temperature fire more effectively thanthe upper layer would without the fillers.

The upper layer incorporates a small amount of gas forming compositionto ensure that an open porosity matrix is formed under fire conditions.In one embodiment, gas formers comprise less than 30% by weight of thecomposition of the upper layer. In another embodiment, gas formerscomprise between about 10% and about 25% by weight of the composition ofthe upper layer. The composition of the upper layer is formulated toswell far less than the lower layer under fire conditions, preferably onthe order of 10% to 100% of its initial thickness. The upper layersuppresses expansion of the lower layer, but it does not preventexpansion of the lower layer.

In presently preferred embodiments, the upper layer is modified toincrease its flexibility and elasticity, as with a flexibilizing agent.In the presently most preferred embodiment, the upper layer includesfrom about 35% to about 65% epoxy resin. The resin is preferablymodified to increase its flexibility and elasticity, illustratively withpolysulfide. It is preferably cured with an amine. Other resins such aspolyamides, polyimides, acrylics, urethanes, polyisocyanurates, and thelike may also be useable. The polysulfide and amine curative componentsof the presently preferred resin give it sufficient flexibility topermit formation of a gas-permeable open porosity matrix on heating andalso permit swelling of the lower layer, particularly in areas ofhighest heating. Only part of the gasses from the lower layer willpermeate through the upper layer. The other part will result in alimited expansion of the lower layer. The upper layer is also resistantto high-temperature stresses produced by having a very high temperatureon the surface of the layer and a much lower temperature underneath it.

Additives may be added to the upper layer to improve its properties inother ways. For example, boron or zinc may be added either in elementalor combined form. Colorants, emissivity controlling agents, rheologymodifying agents, plasticizers, and the like may also be added.

The upper layer also provides advantages to the system when it has notbeen exposed to excessive heat or fire. It makes the system moreresistant to environmental conditions such as water, salt, radiation,and corrosives, and makes it more resistant to physical abrasion. Oneembodiment of the present invention has been successfully tested underthe immersion/freeze/dry cyclic test program delineated in NORSOK M-501Standard (Rev. 4, December 1999), both with and without a topcoat.Samples from that test (without a scribe) have performed as well as asample not subjected to the cyclic test program when tested in sixtyminute hydrocarbon fire endurance tests (Norwegian Petroleum DirectorateStandard NS 3904). These standards are incorporated herein by reference.

Unlike a traditional topcoat, the upper layer of the present inventionhas a substantial thickness, of at least one millimeter, preferably atleast two millimeters, and it is compatible with the composition of thelower layer. In preferred embodiments of the present invention, theupper layer and lower layer include similar resin systems, but differ inthe amounts of gas-forming materials and the amounts of refractoryfillers in them.

Although not preferred in many applications envisioned for the presentinvention, the upper layer may be used without the lower layer in someapplications, such as protecting pipes which do not requirelong-duration protection from fire or other hyperthermal conditions.

It has been found that the composites of the present invention provideat least 30% longer protection under standard jet fire testingprocedures than would be provided by a system including only thecomposition of the upper layer or of the lower layer, even when appliedto the full thickness of the composite system. Preferred systems of thepresent invention provide at least 50% longer protection, and sometimesin excess of 100% longer protection.

The system of the present invention may be utilized to protect a widevariety of substrates. It is particularly useful in protectingstructural steel in hydrocarbon recovery or processing facilities, suchas deep sea drilling platforms and petroleum processing plants. It alsomay be used to protect other substrates, including, by way of example,other metals, plastics, piping, flanges, fins, bulkheads, tanks, rocketlaunch gantries, and the leading edges of hypersonic aircraft.

Other aspects of the present invention will be best be understood inlight of the following description.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

Not applicable.

DETAILED DESCRIPTION OF THE INVENTION

The following detailed description illustrates the invention by way ofexample and not by way of limitation. This description will clearlyenable one skilled in the art to make and use the invention, anddescribes several embodiments, adaptations, variations, alternatives anduses of the invention, including what we presently believe is the bestmode of carrying out the invention.

EXAMPLE 1

A composition for use as an ablative upper layer was prepared containing35% to 65% by weight of a flexible polymeric resin (illustratively amodified epoxy resin, particularly an epoxy polysulfide resin), 5% to30% gas formers (illustratively polyol spumifics, amine blowing agents,and phosphate acid producers), and about 10% to about 40% refractoryfillers. The illustrative composition is a two-component modified epoxyhaving a nominal formula as follows: TABLE 1 Weight percent Melamine 5Ammonium polyphosphate 10 Pentaerythritol 5 Epoxy resin (Bis Phenol A)25 Polysulfide and amine curative 25 Glass fibers (chopped) 5 Ceramicparticles 25

EXAMPLE 2

A lower layer active thermal protective composition was preparedcontaining 30% to 70% by weight of a polymeric resin (illustratively amodified epoxy resin, particularly an epoxy polysulfide resin) and 20%to 50% gas formers (illustratively polyol spumifics, amine blowingagents, and phosphate acid producers). The composition for use in thefollowing tests was a two-component epoxy-based thermally activatedcoating, which when exposed to flame or thermal extreme, volatilizes atfixed temperatures, exhibiting a small volume increase (greater thantwice the original thickness) through the formation of an open cellmatrix, and absorbs and blocks heat to protect the substrate material.The composition included a polyfunctional alcohol, a1,3,5-triazine-2,4,6-triamine, an epoxy resin and a polymer ofbis-(ethylene oxy)methane containing disulfide linkages and curableterminal thiol groups (a polysulfide).

The exemplary composition is a two-component modified epoxy having anominal formula as follows: TABLE 2 Weight percent Melamine 5 Ammoniumpolyphosphate 25 Pentaerythritol 10 Epoxy resin 30 Polysulfide 20 Glassfibers 5 Catalyst 5

A test fixture generally as set out in OTI 95634 dated 1996 was sprayedto a thickness of 3 mm with the lower layer composition.

A graphite fabric was pressed into the lower layer before it set. Thelower layer was allowed to cure for 17 hours, and 3 mm of the upperlayer composition of EXAMPLE 1 was sprayed over the lower layer. Thecomposite was allowed to cure at 30° C. for one month.

EXAMPLE 3

The test article prepared in accordance with EXAMPLE 2 was exposed to ajet fire in accordance with the procedure set out in OTI 95634 dated1996. The test showed that the composite structure providedapproximately sixty minutes of protection under the conditions of thetest.

Smaller scale tests indicate that the composite system provides fargreater protection than the protection given by a thickness of eitherthe upper layer or the lower layer alone equal to the total thickness ofthe composite. The results of those tests are summarized below: TABLE 3Small scale jet fire simulations Temperature circa 1100° C. Heat Fluxcirca 300 kilowatts/m2 Coating Composition: A = lower coating, B = uppercoating Test Article Coating Composition Time to 400° C. Flat Plate 6″ ×6″ × ¼″ 3 mm of A and 3 mm of B 44 minutes 6″ × 6″ × ¼″ 6 mm of A 27minutes Pipe Diameter - 4″ 5 mm of B 10 minutes Diameter - 4″ 3 mm of A,3 mm of B 26 minutes (Wall Thickness: ⅜″)

EXAMPLE 4

A full-scale test of a composite system in accordance with the presentinvention was made in accordance with Offshore Technology Report OTI 95634. Upper layer and lower layer compositions were formed as shown inExample 1 (Table 1) and Example 2 (Table 2). The test specimen wasprimed with an epoxy primer and coated with a nominal thickness of 3 mmof the lower layer composition and a nominal thickness of 3 mm of theupper layer composition reinforced with a sized woven carbon fiberfabric with approximately 2.3 openings per square centimeter. The fabricweighed about 105 grams per square meter, and the joint layers of thecloth were overlapped. The overall thickness of the composite system was6 mm with individual measurements ranging between 5 mm and 7 mm.

At the end of thirty minutes, average box temperature had risen 250° C.above ambient and average web temperature had risen 239° C. Afterseventy-five minutes, average box temperature had risen 327° C. aboveambient and average web temperature had risen 382° C. Maximum rises atthirty minutes were 428° C. and 265° C. respectively; at seventy-fiveminutes they were 450° C. and 411° C.

A test was also made in accordance with Offshore Technology Report OTI95 634 on a system comprising the upper layer composition (Example 1,Table 1) alone. The test specimen was primed with an epoxy primer andcoated with a nominal thickness of 12 mm of the upper layer compositionon the back of the box and 16 mm on the web. The entire structure wasreinforced with a sized woven carbon fiber fabric about 8 mm from thebox and web surface. An additional layer of fabric was used over the webonly at a nominal 12 mm from the web surface. The fabric hadapproximately 2.3 openings per square centimeter, weighed about 105grams per square meter, and the joint layers of the cloth wereoverlapped. The average measured thickness of the system was 12.7 mm(10.5-16 mm) on the back of the box and 15.2 mm (13-17 mm) over the webof the test specimen.

At the end of thirty minutes, average box temperature had risen 121° C.above ambient and average web temperature had risen 175° C. Afterseventy minutes, average box temperature had risen 180° C. above ambientand average web temperature had risen 347° C. After one hundred twentyminutes, average box temperature had risen 207° C. above ambient andaverage web temperature had risen 474° C. Maximum rises at thirtyminutes were 140° C. and 225° C. respectively; at seventy minutes theywere 210° C. and 462° C.; and at one hundred twenty minutes they were239° C. and 628° C. After one hundred twenty minutes, all the fabric wasintact, and no metal substrate had been exposed by the jet fire.

A test was also made in accordance with Offshore Technology Report OTI95 634 on two systems comprising the lower layer composition (Example 2,Table 2) alone. The test specimen was primed with an epoxy primer andcoated with a nominal thickness of 5 mm of the lower layer composition(test A) and 11 mm of the lower layer composition (test B). In eachtest, the entire structure was reinforced with a 19-gauge wire mesh with12.7×12.7 mm openings pinned to the substrate. The average measuredthickness of the system for test A was 4 mm (2.5-5 mm) on the back ofthe box and 4.7 mm (3-7 mm) over the web of the test specimen. Theaverage measured thickness of the system for test B was 11 mm (9-14 mm)on the back of the box and 11.4 mm (9-13 mm) over the web of the testspecimen.

At the end of thirty minutes, average box temperature of test A hadrisen 352° C. above ambient and average web temperature had risen 473°C.

At the end of thirty minutes, average box temperature of test B hadrisen 200° C. above ambient and average web temperature had risen 180°C. After seventy-four minutes, average box temperature had risen 318° C.above ambient and average web temperature had risen 325° C. Maximumrises at seventy-four minutes were 604° C. and 376° C. Metal mesh andmetal substrate had been exposed by the jet fire.

In view of the above, it will be seen that the several objects andadvantages of the present invention have been achieved and otheradvantageous results have been obtained.

As various changes could be made in the above constructions withoutdeparting from the scope of the invention, it is intended that allmatter contained in the above description or shown in the accompanyingdrawings shall be interpreted as illustrative and not in a limitingsense.

1. A thermally protective composition comprising a polymeric binder, aflexibilizing agent, from 10% to 30% of a blowing agent which changesfrom solid to gas at a hyperthermal temperature to which the compositionmay be subjected, and at least 20% by weight of a refractory filler. 2.The composition of claim 1 wherein the binder is an epoxy resin modifiedwith the flexibilizing agent, the composition comprising about 35% toabout 65% by weight of the modified epoxy resin.
 3. The composition ofclaim 2 wherein the flexibilizing agent comprises polysulfide, andwherein the modified epoxy resin is cured with an amine.
 4. Thecomposition of claim 1 wherein the filler comprises both particles andfibers.
 5. The composition of claim 1 wherein the filler comprisesceramic particles and glass fibers.
 6. The composition of claim 1wherein the filler comprises one or more materials selected from thegroup consisting of glass, graphite, and ceramic.
 7. The composition ofclaim 1 wherein the filler comprises at least 25% by weight of thecomposition.
 8. The composition of claim 7 wherein the filler comprisesabout 25% to 40%, by weight of the composition.
 9. A thermallyprotective composition comprising a polymeric binder, a blowing agent,and at least 7% by weight of the composition of a refractory filler, thecomposition responding to hyperthermal conditions by expanding about 10%to about 100% and forming an open cell matrix.
 10. The composition ofclaim 9 wherein the refractory filler comprises both particles andfibers.
 11. The composition of claim 9 wherein the filler comprisesceramic particles and glass fibers.
 12. The composition of claim 9wherein the filler comprises one or more materials selected from thegroup consisting of glass, graphite, and ceramic.
 13. The composition ofclaim 9 wherein the filler comprises at least about 15% by weight of thecomposition.
 14. The composition of claim 9 wherein the filler comprisesabout 25% to 30%, by weight of the composition.
 15. The composition ofclaim 9 wherein the blowing agent comprises 10% to 30% by weight of thecomposition.
 16. The composition of claim 9 comprising a flexibilizingagent.
 17. The composition of claim 16 wherein the composition comprisesabout 35% to about 65% modified epoxy resin.
 18. The composition ofclaim 17 wherein the epoxy resin is modified with polysulfide and curedwith an amine.
 19. A method for protecting a substrate from hyperthermalconditions comprising a first step of applying a layer of a firstpolymeric active thermal protective composition to the substrate,thereafter a second step of applying to the first layer an upper layerof a second polymeric thermal protective composition which when exposedto a fire or other hyperthermal condition swells to form an open cellmatrix to permit passage of gasses from the lower layer to ambient, thesecond composition comprising a fill of a refractory material comprisingat least about seven percent of the second composition by weight, and astep of embedding a mesh or fabric reinforcement in the system.
 20. Themethod of claim 19 wherein both the first composition and the secondcomposition comprise a polymeric binder and a gas former, the secondcomposition comprising less gas former by weight than the firstcomposition, the method providing a composite system overlying thesubstrate.
 21. The method of claim 20 wherein the upper layer is anepoxy resin modified to increase its flexibility and elasticity.
 22. Themethod of claim 20 wherein the reinforcement comprises a graphitefabric.
 23. The method of claim 20 wherein the reinforcement comprises ametal mesh.
 24. The method of claim 19 wherein lower layer is applied toa cured thickness of about one to about twenty-five mm.
 25. The methodof claim 24 wherein the lower layer is less than 15 mm thick.
 26. Themethod of claim 19 wherein the lower layer responds to hyperthermalconditions by expanding to at least twice its original thickness. 27.The method of claim 19 wherein the upper layer is applied to a curedthickness of about one to about fifteen mm.
 28. The method of claim 27wherein the upper layer is less than about six mm thick.
 29. The methodof claim 19 wherein the upper layer responds to hyperthermal conditionsby expanding to an average thickness no more than twice its originalthickness.